Crystallization of Bottlebrush Statistical Copolymers of Polystyrene and Poly(ethylene oxide)

Gan, Xuchen; Seong, Hong-Gyu; Hu, Mingqiu; Chen, Zhan; Emrick, Todd; Russell, Thomas P.

doi:10.1021/acs.macromol.4c01159

Crystallization of Bottlebrush Statistical Copolymers of Polystyrene and Poly(ethylene oxide)

Journal Article · Tue Jul 16 00:00:00 EDT 2024 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.4c01159· OSTI ID:2429609

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University of Massachusetts, Amherst, MA (United States)
University of Massachusetts, Amherst, MA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Here, bottlebrush statistical copolymers (BSCPs) with poly(ethylene oxide) (PEO) and polystyrene (PS) side chains grafted to a polynorbornene (PNB) backbone were synthesized by ring-opening metathesis polymerization (ROMP). The impact of the glassy PS side chains on the crystallization of the PEO side chains as a function of the backbone length, grafting densities, and fraction of the PS and PEO side chains is described. The bottlebrush architecture, where the side chains are anchored to the backbone, inherently constrains the mobility of PEO. Compared with the bulk crystallization temperature of PEO, the higher glass transition temperature of PS places further constraints on PEO crystallization. The limited mobility of PEO leads to cold crystallization behavior during heating. Reduced grafting densities, in turn, reduce side-chain crowding, leading to less extended pendant structures. The degree of crystallinity of PEO was found to decrease at lower grafting densities to a point where crystallization was not observed. The average distance between bottlebrush backbones increased linearly with the backbone length, suggesting that the backbone forms a distinct mesodomain. For BSCPs with asymmetric volume fractions of PS and PEO side chains, the degree of crystallinity of PEO increases with a change from cold crystallization to normal nucleation and growth during cooling, as a result of reduced constraints on PEO mobility by the glassy PS side chains.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: US Air Force Office of Scientific Research (AFOSR); US Army Research Office (ARO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2429609

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 15 Vol. 57; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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